Intermolecular Coupling of Alkynes with Acrylates by Recyclable Oxide-Supported Ruthenium Catalysts: Formation of Distorted Ruthenium(IV)-oxo Species on Ceria as a Key Precursor of Active Species
Intermolecular Coupling of Alkynes with Acrylates by Recyclable Oxide-Supported Ruthenium Catalysts: Formation of Distorted Ruthenium(IV)-oxo Species on Ceria as a Key Precursor of Active Species
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DOI：
10.1002/adsc.201100415
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发表时间：
2011-10
影响因子：
5.4
通讯作者：
H. Miura;Shun Shimura;S. Hosokawa;S. Yamazoe;K. Wada;M. Inoue
中科院分区：
文献类型：
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作者：
H. Miura;Shun Shimura;S. Hosokawa;S. Yamazoe;K. Wada;M. Inoue
固体氧化铈负载的钌催化剂（Ru/CeO 2）以及氧化锆负载的钌催化剂（Ru/ZrO 2）对炔与丙烯酸酯的分子间偶联表现出高活性，以高产率得到相应的1，3-二烯。反应在甲酸钠存在下进行，内炔或末端炔和异炔烯均可用于催化体系。该固体钌催化剂可循环使用多次而活性无明显损失。红外光谱和X射线吸收精细结构（XAFS）研究表明，氧化铈负载的钌催化剂在反应的初始阶段发生了畸变，钌（IV）-氧物种转变为低价钌物种，这对偶联反应是有效的。
A solid ceria-supported ruthenium catalyst (Ru/CeO2) as well as a zirconia-supported ruthenium catalyst (Ru/ZrO2) showed high activities toward the intermolecular coupling of alkynes with acrylates to give the corresponding 1,3-dienes in high yields. The reaction proceeded in the presence of sodium formate and both internal or terminal alkynes and norbornene could be applied for the catalytic systems. The solid ruthenium catalyst could be recycled for several times without significant loss of activity. The FT-IR and X-ray absorption fine structure (XAFS) studies of ceria-supported ruthenium catalysts showed that a distorted ruthenium(IV)-oxo species on ceria was transformed during the initial stage of the reaction into a low-valent ruthenium species that was effective for the coupling reactions.